Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G15/00—Apparatus for electrographic processes using a charge pattern
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0525—Coating methods
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0528—Macromolecular bonding materials
  • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
  • G03G5/0535—Polyolefins; Polystyrenes; Waxes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0528—Macromolecular bonding materials
  • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
  • G03G5/0546—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0528—Macromolecular bonding materials
  • G03G5/0589—Macromolecular compounds characterised by specific side-chain substituents or end groups
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0528—Macromolecular bonding materials
  • G03G5/0596—Macromolecular compounds characterised by their physical properties
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/14—Inert intermediate or cover layers for charge-receiving layers

Definitions

• the present invention relates to a method of
• Some of the photosensitive layers are a lamination type including a charge-generating layer containing a charge-generating material and a charge- transporting layer containing a charge-transporting material.
• the charge-transporting layer is formed as a uniform layer by a method where a coating film is formed by application of a coating liquid prepared by
• PTLs 1 and 2 disclose techniques of providing ununiform charge-transporting layers in order to obtain high-gamma electrophotographic photosensitive members. reduce residual potentials, and maintain high image qualities for a long time.
• a coating film is formed by application of a dispersion solution prepared by dispersing charge-transporting pigment particles in a solution (polymer solution) in which a polymer is dissolved in a solvent and drying the resulting coating.
• PTL 3 discloses a method of forming an intermediate layer of an electrophotographic photosensitive member using a dispersion solution prepared by dispersing charge- transporting pigment particles (electron-transporting pigment particles) in a polymer emulsion.
• the present invention provides a method of
• the present invention relates to a method of producing an electrophotographic photosensitive member comprising a charge-transporting layer, and the method includes a step of forming a coating film by applying a dispersion solution comprising polyolefin polymer particles and charge-transporting pigment particles as dispersoids and comprising a dispersion medium, and then forming the charge- transporting layer by heating the coating film and melting the polyolefin polymer particles, wherein, the particles consisting of the polyolefin polymer particles and the charge-transporting pigment particles in the dispersion solution have a number average particle diameter of 50 nm or more and 300 nm or less and a degree of dispersion (standard deviation/number average particle diameter) of 1.0 or less.
• the present invention can provide a method of producing an electrophotographic photosensitive member using a dispersion solution that shows high liquid stability in long-period storage and hardly causes aggregation of charge- transporting pigment particles during drying a coating.
• Fig. 1 is a diagram illustrating an example of the layer structure of an electrophotographic photosensitive member .
• Fig. 2 is a diagram illustrating an example of the layer structure of an electrophotographic photosensitive member .
• the dispersion solution, according to the present invention, containing polyolefin polymer particles and charge-transporting pigment particles, as dispersoids, and a dispersion medium is a solution in which both the polyolefin polymer particles and the charge-transporting pigment particles are dispersed in the dispersion medium.
• the charge-transporting pigment particles that are used in the present invention are of a charge-transporting compound insoluble in the dispersion medium of the
• the dispersion medium of the dispersion solution is water
• a charge-transporting compound insoluble in water is the charge-transporting pigment particles that are used in the present invention.
• Examples of the charge-transporting compound include hydrazine compounds, triarylamine compounds,
• stilbene compounds quinone compounds, imide compounds, benzimidazole compounds, cyclopentadienylidene compounds, and azo compounds .
• charge-transporting compounds will be described below.
• charge-transporting compounds represented by the following Formulae (1) to (9) and high molecular weighted charge-transporting compounds thereof can be particularly used.
• the charge-transporting compounds represented by the following Formulae (1) to (9) are electron-transporting compounds.
• Examples of the imide compound include compounds having a cyclic imide structure.
• the imide compound may have a condensed aromatic ring structure. Specific examples thereof include compounds represented by the following
• R 1 and R 2 each independently represents a substituted or unsubstituted alkyl, phenyl, or pyridyl group, the substituent of which is an alkyl group, a haloalkyl group, a hydroxyalkyl group, a halogen atom, a hydroxy group, a carboxy group, an alkoxy group, a cyano group, a nitro group, a phenyl group, or a phenyldiazenyl group; and n 1 is 1 or 2.
• Examples of the benzimidazole compound include compounds having a benzimidazole ring structure.
• the benzimidazole compound may have a condensed aromatic ring structure. Specific examples thereof include compounds represented by any of the following Formulae (2) to (4):
• R 3 to R 6 each independently represents a hydrogen atom, a halogen atom, or an alkyl group; and n 2 is 1 or 2.
• R 7 to R 10 each independently represents a hydrogen atom, a halogen atom, or an alkyl group; and n 3 is 1 or 2.
• R and R each independently represents a hydrogen atom, a halogen atom, a nitro group, or an alkyl group; R 13 represents a substituted or
• substituent of which is an alkyl group, a haloalkyl group, a hydroxyalkyl group, a halogen atom, a hydroxy group, a carboxy group, a nitro group, or a cyano group; and n 4 is 1 or 2.
• Examples of the quinone compound include compounds having a para-quinoid structure or an ortho-quinoid structure.
• the quinone compound may have a condensed aromatic ring structure or a structure where quinoid
• R 31 represents an oxygen atom or dicyanomethylene group
• R 32 to R 39 each independently
• X 21 and X 22 each independently represents a carbon atom or a nitrogen atom, wherein when X is a nitrogen atom, R 36 does not exist, and when X 22 is a nitrogen atom, R 35 does not exist.
• R 40 and R 49 each independently represents an oxygen atom or a dicyanomethylene group
• R 41 to R 48 each independently represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, or a carboxy group
• X 31 and X 32 each independently represents a carbon atom or a nitrogen atom, wherein when X 31 is a nitrogen atom, R 47 does not exist, and when X 32 is a nitrogen atom, R 43 does not exist .
• Examples of the cyclopentadienylidene compound include compounds having a cyclopentadienylidene structure.
• the cyclopentadienylidene compound may have a condensed aromatic ring structure. Specific examples thereof include compounds represented by the following Formula (8): [0036]
• R represents an oxygen atom, a dicyanomethylene group, or a substituted or unsubstituted phenylimino group, the substituent of which is an alkyl group
• R 23 to R 30 each independently represents a hydrogen atom, an alkoxycarbonyl group, or a nitro group
• X 11 and X 12 each independently represents a carbon atom or a nitrogen atom, wherein when X 11 is a nitrogen atom, R 27 does not exist, and when X 12 is a nitrogen atom, R 26 does not exist.
• Examples of the azo compound include compounds having an azo group. Specific examples thereof include compounds represented by the following Formula (9):
• R 63 represents a fluorenonediyl group, a diphenyloxadiazolediyl group, or an
• R 61 and R 62 independently present a monovalent group having a structure represented by the following Formula (10) or (11): [0041]
• R 51 to R 55 each independently represents a hydrogen atom, a halogen atom, or an alkyl group; and m is 1 or 2.
• alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group .
• the haloalkyl group means an alkyl group
• halogen atom substituted by a halogen atom
• examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups that are each substituted by a fluorine, chlorine, bromine, or iodine atom.
• the hydroxyalkyl group means an alkyl group substituted by a hydroxy group, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups that are each substituted by a hydroxy group.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, a nonoxy group, a decoxy group, an undecoxy group, and a dodecoxy group.
• charge-transporting compound (charge-transporting compound) can be obtained as follows.
• the compound represented by Formula (1) can be synthesized by, for example, a method described in U.S. Patent No. 4,442,193, U.S. Patent No. 4,992,349, or U.S.
• the compound can be synthesized by a reaction of naphthalenetetracarboxylic acid dianhydride, which can be purchased from Tokyo Chemical
• the compound represented by Formula (2) and the compound represented by Formula (3) can be synthesized by, for example, a method described in U.S. Patent No. 4,442,193, U.S. Patent No. 4,992,349, or U.S. Patent No. 5,468,583 by using a 1 , 2-dianiline derivative instead of the monoamine derivative.
• the 1 , 2-dianiline derivative can be purchased from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan K.K., or Johnson Matthey Japan Inc. as a reagent.
• the compound represented by Formula (4) can be synthesized by, for example, a method described in Japanese Patent Laid-Open No. 2004-093791 or Japanese Patent Laid- Open No. 7-89962.
• the compound can be synthesized by, for example, a method described in Japanese Patent Laid-Open No. 2004-093791 or Japanese Patent Laid- Open No. 7-89962.
• the compound can be synthesized by, for example, a method described in Japanese Patent Laid-Open No. 2004-093791 or Japanese Patent Laid- Open No. 7-89962.
• the compound can be synthesized by, for example, a method described in Japanese Patent Laid-Open No. 2004-093791 or Japanese Patent Laid- Open No. 7-89962.
• the compound can be synthesized by, for example, a method described in Japanese Patent Laid-Open No. 2004-093791 or Japanese Patent Laid- Open No. 7-89962.
• the compound can be synthesized by,
• the compound represented by Formula (5) can be synthesized by, for example, a method described in Japanese Patent Laid-Open No. 1-206349 or the Proceedings of
• the compound can be synthesized using a phenol derivative as a raw material, which can be purchased from Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Japan K.K. as a reagent.
• the compound represented by Formula (6) can be purchased from, for example, Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan K.K., or Johnson Matthey Japan Inc. as a reagent or can be synthesized by a method described in Bull. Chem. Soc. Jpn. , Vol. 65, pp. 116-1011 (1992) or Chem. Educator, No. 6, pp. 227-234 (2001) using a commercially available phenanthrene derivative or phenanthroline
• a substituent can be introduced to a halide of the phenanthrene derivative or the
• phenanthroline derivative described in these documents by, for example, a cross-coupling reaction using a palladium catalyst .
• a dicyanomethylene group can also be introduced into such a compound by a reaction between the compound and malononitrile .
• the compound represented by Formula (7) can be purchased from, for example, Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan K.K., or Johnson Matthey Japan Inc. as a reagent or can be synthesized by a method described in Synthesis, Vol. 5, pp. 388-389 (1988) using commercially available compounds .
• a dicyanomethylene group can also be introduced into such a compound by a reaction between the compound and malononitrile .
• the compound represented by Formula (8) can be purchased from, for example, Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan K.K., or Johnson Matthey Japan Inc. as a reagent or can be synthesized by a method described in Japanese Patent Laid-Open No. 5-279582, U.S. Patent No.
• the compound represented by Formula (9) can be synthesized by, for example, a method described in Journal of the Imaging Society of Japan, Vol. 37, No. 3, pp. 280-288 (1998) .
• the polyolefin polymer of the polyolefin polymer particles that are used in the present invention is a
• the polyolefin polymer may be a polymer obtained by polymerization of olefin only or a polymer (copolymer) obtained by copolymerization of olefin and another monomer.
• the polyolefin polymer that is used in the present invention can include the following (Al), (A2), and (A3) in a mass ratio satisfying the following expression:
• (Al) is a repeating structural unit represented by the following Formula (121):
• R 121 to R 124 each independently represents a hydrogen atom or an alkyl group.
• (A2) is a repeating structural unit represented by the following Formula (131) or (132):
• R 131 to R 134 each independently represents a hydrogen atom, an alkyl group, a phenyl group, or a monovalent group represented by -Y 131 COOH (Y 131 represents a single bond, an alkylene group, or an arylene group), wherein at least one of R 131 to R 134 is a monovalent group represented by -Y 131 COOH; R 135 and R 136 each independently represents a hydrogen atom, an alkyl group, or a phenyl group; and X 131 represents a divalent group represented by -Y 132 COOCOY 133 - (Y 132 and Y 133 each independently represents a single bond, an alkylene group , or an arylene grou ) .
• (A3) is a repeating structural unit represented by the following Formula (141), (142), (143), or (144):
• R to R each independently represents a hydrogen atom or a methyl group
• R 151 to R 153 each independently represents an alkyl group having 1 to 10 carbon atoms
• R to R each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
• alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
• alkylene group examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group .
• Examples of the arylene group include a phenylene group, a biphenylene group, and a naphthylene group.
• R 121 to R 124 can be hydrogen atoms.
• the repeating structural unit represented by Formula (121) can be introduced into the polyolefin polymer by a
• R 131 and R 133 can be hydrogen atoms; R 132 can be a hydrogen atom or a methyl group; and R 134 can be a monovalent group represented by -COOH (carboxy group ) .
• R 135 can be a hydrogen atom; and R 136 can be a hydrogen atom or a methyl group.
• unsaturated carboxylic acid and/or its anhydride can be introduced into the polyolefin polymer by a polymerization reaction in the presence of a monomer having at least one carboxy group and/or at least one acid anhydride group in the molecule ( in the monomer unit ) .
• the monomer include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and half esters and half amides of
• acrylic acid, methacrylic acid, or maleic acid (anhydride), in particular, acrylic acid or maleic anhydride can be used.
• R 151 can be a methyl group or an ethyl group.
• the repeating structural unit represented by Formula (141) can be introduced into the polyolefin polymer by a polymerization reaction in the presence of a
• (meth)acrylate monomer examples include methyl (meth) acrylate , ethyl (meth)acrylate, and butyl
• R 152 and R 153 can be methyl groups, ethyl groups, or butyl groups.
• the repeating structural unit represented by Formula (142) can be introduced into the polyolefin polymer by a polymerization reaction in the presence of a maleate ester monomer. Examples of the monomer include dimethyl maleate, diethyl maleate, and butyl maleate .
• R 161 and R 162 can be hydrogen atoms.
• the repeating structural unit represented by Formula (143) can be introduced into the polyolefin polymer by a
• R 163 can be a methyl group or an ethyl group.
• the repeating structural unit represented by Formula (144) can be introduced into the polyolefin polymer by a polymerization reaction in the presence of an
• alkylvinyl ether monomer and a vinyl alcohol monomer.
• Examples of the monomer include vinyl alcohols obtained by saponification of methyl vinyl ether, ethyl vinyl ether, or vinyl ester with a basic compound.
• Formula (141) can be particularly used.
• polyolefin polymer particles can be easily reduced by
• liquid stability in the case of storing the dispersion solution for a long time is further improved by adjusting the ratio of (A1)/(A3) to 55/45 or more, and the particle diameter of the polyolefin polymer particles can be reduced by adjusting the ratio of (A1)/(A3) to 99/1 or less.
• (Al) is a repeating structural unit represented by Formula (121) where R 121 to R 124 are hydrogen atoms; (A2) is a repeating
• a carboxylic anhydride structure derived from, for example, maleic anhydride forms an acid anhydride structure by cyclodehydration of two adjacent carboxy groups.
• a dispersion solution containing a basic compound partial or full ring opening of the anhydride groups occurs to easily form a structure of a carboxy group or its salt.
• the polyolefin polymer that is used in the present invention may contain a repeating structural unit derived from a monomer other than the above-mentioned monomers.
• the content of the repeating structural unit derived from the monomer other than the above-mentioned monomers can be 20 mass% or less based on the total mass of the polyolefin polymer.
• optional monomers include alkyl vinyl ethers having 3 to 30 carbon atoms, such as methyl vinyl ether and ethyl vinyl ether, dienes,
• the polyolefin polymer that is used in the present invention may be a synthesized polymer or a commercially available polymer.
• the polyolefin polymer can be obtained by, for example, high-pressure radical copolymerization of monomers (such as olefin monomers) for synthesizing the polyolefin polymer in the presence of a radical generator.
• monomers such as olefin monomers
• a radical generator for synthesizing the polyolefin polymer in the presence of a radical generator.
• the method of synthesizing the polyolefin polymer is described in, for example, the chapters 1 to 4 of New Polymer Experiment 2 Synthesis and Reaction of Polymer (1) (Kyoritsu Shuppan Co., Ltd.), Japanese Patent Laid-Open No. 2003-105145, or
• Examples of the commercially available polyolefin polymers include “BONDINE (trade name)” manufactured by Sumitomo Chemical Co., Ltd. and “Primacor (trade name)” manufactured by The Dow Chemical Company.
• dispersion solution for charge-transporting layer can be prepared by dispersing polyolefin polymer particles in water as a dispersion medium, then adding charge-transporting pigment particles to the resulting dispersion solution, and further subjecting the resulting mixture to dispersion treatment. This method will be described in detail below.
• the dispersion solution of polyolefin polymer particles can be prepared by, for example, heating and mixing (dispersion treatment) a polyolefin polymer, water as the dispersion medium, and, optionally, an organic solvent in a sealable disperser.
• the shape of the polyolefin polymer in such a method is not particularly limited, but particles having a diameter of 1 cm or less (such as 0.8 cm or less) can be used from the viewpoint of increasing the particle-forming rate.
• the disperser an apparatus that has a tank in which a liquid can be put and can moderately stir the
• a disperser examples include a
• a disperser that can apply a pressure of 0.1 MPa or more can be used.
• Polyolefin polymer particles as the dispersoid and water as the dispersion medium (and an optional organic solvent) are put in the tank of a disperser and are mixed by stirring at 40° C or less for example. Then, the stirring (dispersion treatment) is continued while maintaining the temperature inside the tank at 50 to 200° C, preferably 60 to 200° C, for 5 to 120 minutes to obtain a dispersion solution of the polyolefin polymer particles.
• a disperser preferably 60 to 200° C, for 5 to 120 minutes
• compound to be added can be 0.5 to 3.0 equivalents , such as 0.8 to 2.5 equivalents or 1.0 to 2.0 equivalents, to the carboxy groups (one mole of the acid anhydride group is regarded as two moles of the carboxy group) in the
• polyolefin polymer In an amount of 0.5 equivalents or more. the effect of the basic compound is high, and in an amount of 3.0 equivalents or less, the time for heating a coating can be shortened, and coloring of the dispersion solution due to the basic compound can be prevented.
• the basic compound can be a compound that volatiles during heating of a coating of the dispersion solution.
• organic amine compounds examples include triethylamine, N,N-dimethylethanolamine, aminoethanolamine , N-methyl-N , N-diethanolamine ,
• diethylamine 3-ethoxypropylamine , 3-diethylaminopropylamine , sec-butylamine, propylamine, methylaminopropylamine ,
• a dispersion solution for charge-transporting layer that is used in the present invention can be obtained by adding charge-transporting pigment particles to the thus- prepared dispersion solution of polyolefin polymer particles and further performing dispersion treatment .
• the dispersion treatment can be performed by, for example, using a disperser such as a paint shaker, a ball mill, a sand mill, an ultrasonic disperser, a high-pressure homogenizer, a stirrer, a mixer, or an agitator.
• a disperser such as a paint shaker, a ball mill, a sand mill, an ultrasonic disperser, a high-pressure homogenizer, a stirrer, a mixer, or an agitator.
• At least one of the dispersion media used in the dispersion solution for charge-transporting layer according to the present invention can be water. From the viewpoint of improving coatability (inhibition of dewetting) of the dispersion solution for charge-transporting layer, a
• dispersion medium including both water and an organic compound
• organic solvent can be used.
• organic solvent examples of the organic solvent
• ketones such as methyl ethyl ketone, acetone, and diethyl ketone
• alcohols such as propanol, butanol, methanol, and ethanol
• ethers such as tetrahydrofuran , dioxane, and ethylene glycol monobutyl ether.
• alcohols can be used.
• the addition of the organic solvent can be performed during preparation of the dispersion
• the amount of water can be 50 mass% or more based on the total mass of the water and the alcohol.
• the mass ratio of water can be adjusted to 50 nm or more and 300 nm or less, and the degree of dispersion (standard deviation/number average particle diameter) of the particles can be easily adjusted to 1.0 or less.
• the particles and the charge-transporting pigment particles (the amount of particles composed of the polyolefin polymer particles and the charge-transporting pigment particles) contained in the dispersion solution of the charge- transporting layer according to the present invention can be 7 mass% or more and 20 mass% or less based on the total mass of the dispersion solution for charge-transporting layer.
• the mass ratio of the polyolefin polymer particles and the charge-transporting pigment particles can be 7% or more and 20% or less, the number average particle diameter of the particles composed of the polyolefin polymer particles and the charge-transporting pigment particles can be easily adjusted to 300 nm or less.
• polyolefin polymer particles and the charge-transporting pigment particles contained in the dispersion solution for charge-transporting layer is 50 nm or more and 300 nm or less, and the degree of dispersion (standard
• deviation/number average particle diameter is 1.0 or less. That is, the difference between the particle diameters of the polyolefin polymer particles and the charge-transporting pigment particles is small. Consequently, precipitation of the charge-transporting pigment particles is prevented.
• liquid stability in the case of storing the dispersion solution for charge- transporting layer for a long time is high, and aggregation of the charge-transporting pigment particles during
• Charge-transporting pigment particles (charge- transporting compound) generally include an aromatic ring having a high cohesive force in its molecule and are thereby tend to aggregate in a solution. Therefore, the charge- transporting pigment particles easily aggregate in a coating liquid where a binder resin is dissolved in a solvent, and the liquid stability (dispersion stability) tends to be insufficient.
• the present inventors have investigated and have found that the cohesive force of the charge-transporting pigment particles can be reduced, without dissolving a binder resin in a solvent, by letting polyolefin polymer particles present at surroundings of the charge-transporting pigment particles.
• the liquid stability can be improved to some extent by the presence of the polyolefin polymer particles, but the presence of the polyolefin polymer particles alone cannot sufficiently prevent (a) aggregation of the charge- transporting pigment particles during melting of the polyolefin polymer particles and (b) precipitation of the charge-transporting pigment particles due to gravity during the storage of the dispersion solution for charge- transporting layer for a long time.
• hindrance effect is believed to sufficiently prevent aggregation of the charge-transporting pigment particles in the dispersion solution for charge-transporting layer and sufficiently reduce the cohesive force of the charge- transporting pigment particles during melting of the polyolefin polymer particles.
• the particle diameter of the particles composed of the polyolefin polymer particles and the charge-transporting pigment particles is measured by observing a prepared dispersion solution using a transmission electron microscope (TEM) . Specifically, the dispersion solution is frozen and is observed using a TEM equipped with an energy filter having a cryo-transfer .
• TEM transmission electron microscope
• the number average particle diameter and the degree of dispersion can be determined by measuring 200 particles randomly selected from the particles composed of the
• polyolefin polymer particles and the charge-transporting pigment particles without distinction.
• the particles composed of the polyolefin polymer particles and the charge-transporting pigment particles are a mixture (a group of particles) of two types of particles, the polyolefin polymer particles and the charge-transporting pigment particles.
• the two types of particles contained in the particle mixture are equally treated without
• number average particle diameter refers to the length of an edge of a particle when the particle is a so-called normal crystal such as a cube or an octahedron.
• the number average particle diameter is determined using the diameter of a sphere having the same volume as that of the particle.
• the TEM is set to a magnification of 5000- to
• the TEM is set to an application voltage of 80 to 200 kV.
• Images obtained by the TEM are recorded on films, and the image on each film is resolved into 2048 x 2048 pixels and is subjected to image processing by a computer.
• image processing by a computer.
• the image is converted into a digital image with a scanner, and shading correction and contrast/edge enhancement are performed as needed. Then, a histogram is drawn, and
• particle images are extracted by binary processing to
• dispersion solution for charge-transporting layer can be performed by various methods that are used in the field of electrophotographic photosensitive member. Among such
• dip coating can be particularly employed.
• the application in the case of performing dip coating of the dispersion solution for charge- transporting layer, the application can be performed with a dip coater set to an environment of a relative humidity of 60% or less at 23° C and a wind velocity of 1 m/s or less.
• the electrophotographic photosensitive member generally includes a support and a photosensitive layer disposed on the support. Furthermore, in many cases, a conductive layer or an undercoat layer is disposed between the support and the photosensitive layer, or the
• photosensitive layer may be a multilayer type where a charge-generating layer and a charge-transporting layer (hole-transporting layer) are laminated. Furthermore, a technique of using the undercoat layer between the support and the photosensitive layer as a charge-transporting layer (electron-transporting layer) by imparting a charge- transporting ability (electron-transporting ability) to the layer is known.
• the undercoat layer is also called an intermediate layer or a barrier layer.
• the thickness of the charge- transporting layer can be 0.1 to 20 ⁇ , such as 0.3 to 5 ⁇ .
• a reference numeral 101 denotes a support
• a reference numeral 102 denotes a charge-transporting layer serving as the undercoat layer in the present invention
• a reference numeral 103 denotes a charge-generating layer
• a reference numeral 104 denotes a charge-transporting layer
• a reference numeral 105 denotes a photosensitive layer ( laminate-type photosensitive layer).
• the thickness of the charge- transporting layer can be 1 to 50 ⁇ , such as 3 to 30 ⁇ .
• a reference numeral 201 denotes a support, a
• reference numeral 202 denotes an undercoat layer
• reference numeral 203 denotes a charge-generating layer
• a reference numeral 204 denotes a charge-transporting layer of the present invention
• a reference numeral 205 denotes a photosensitive layer ( laminate-type photosensitive layer).
• the temperature for heating a coating of the dispersion solution for charge-transporting layer according to the present invention can be 80 to 120° C.
• the polyolefin polymer particles can be sufficiently molten as long as the temperature is 80° C or more, and shrinking of the coating film (charge-transporting layer) due to heating can be prevented as long as the temperature is 120° C or less.
• the support that is used in the electrophotographic photosensitive member may be any conductive substance
• conductive support examples thereof include metal and alloy supports such as aluminum, aluminum alloy, nickel, copper, gold, iron, and stainless steel supports.
• the support may be those having a metal thin film, such as aluminum, silver, or gold film, or a conductive material film, such as indium oxide or tin oxide film, on an insulating support, such as a polyester, polycarbonate, polyimide, or glass support.
• a metal thin film such as aluminum, silver, or gold film
• a conductive material film such as indium oxide or tin oxide film
• a conductive layer may be disposed between the support and the photosensitive layer in order to prevent interference fringes due to scattering of, for example, laser beams and to cover damages of the support .
• the conductive layer can be formed by dispersing conductive particles such as carbon black particles , metal particles, or metal oxide particles in a binder resin.
• the metal oxide particles include particles of metal oxides such as zinc oxide and titanium oxide.
• the conductive particles barium sulfate particles covered with oxygen-deficiency-type tin oxide also can be used.
• the conductive layer may further contain a leveling agent for improving the surface flatness of the conductive layer .
• An undercoat layer may be disposed between the support or the conductive layer and the photosensitive layer in order to, for example, improve the adhesiveness.
• a charge-transporting layer according to the present invention may be used as the undercoat layer.
• the undercoat layer can be formed by applying a coating liquid for undercoat layer prepared by dissolving a polymer in a solvent and drying the resulting coating.
• polymers that is used in the undercoat layer include casein, polyvinyl alcohol, and
• polyamide e.g.. Nylon 6, Nylon 66, Nylon 610, copolymer nylon, and alkoxy methylated nylon
• the charge-transporting layer as the undercoat layer can be formed as described above, and the charge-transporting pigment particles can be electron-transporting pigment particles .
• a photosensitive layer is disposed on the support, the conductive layer, or the undercoat layer.
• the photosensitive layer may be a monolayer-type photosensitive layer containing a charge-generating material and a charge-transporting material in single layer or may be a laminate-type photosensitive layer where a charge- generating layer containing charge-generating material and a charge-transporting layer containing a charge-transporting material are laminated. From the viewpoint of
• the laminate-type photosensitive layer in particular, a laminate-type photosensitive layer where a charge-generating layer and a charge-transporting layer are laminated in this order from the support side (forward lamination-type photosensitive layer) can be used.
• forward lamination-type photosensitive layer a laminate-type photosensitive layer where a charge-generating layer and a charge-transporting layer are laminated in this order from the support side
• the charge-transporting layer can be a hole-transporting layer containing a hole-transporting material (hole-transporting compound) as the charge- transporting material.
• the laminate-type photosensitive layer will be described below.
• the charge-generating layer can be formed by applying a coating liquid for charge-generating layer prepared by dispersion treatment of a charge-generating material together with a binder resin and a solvent and dying the resulting coating.
• Examples of the charge-generating material that is used in the present invention include azo pigments such as monoazo, disazo, and trisazo; phthalocyanine pigments such as metal phthalocyanine and non-metal phthalocyanine; indigo pigments such as indigo and thioindigo; perylene pigments such as perylene acid anhydride and perylene acid imide; polycyclic quinone pigments such as anthraquinone and pyrenequinone ; squarilium coloring matters; pyrylium salts and thiapyrylium salts; triphenylmethane coloring matters; inorganic materials such as selenium, selenium-tellurium, amorphous silicon, cadmium surfide, and zinc oxide;
• quinacridone pigments include quinacridone pigments; azlenium salt pigments; cyanine dyes; xanthene coloring matters; quinonimine coloring matters; and styryl coloring matters.
• metal phthalocyanine pigments in particular, oxytitanium phthalocyanine, chlorogallium phthalocyanine, dichlorotin phthalocyanine, and hydroxygallium
• phthalocyanine can be used. Above all, hydroxygallium phthalocyanine can be used.
• polyurethane polymers silicone polymers, alkyd polymers, epoxy polymers , cellulose polymers , and melamine polymers .
• butyral polymers can be used.
• the charge-transporting layer according to the present invention can be used as the charge-transporting layer of a laminate-type photosensitive layer and can be formed by the method described above. In the case of using a charge-transporting layer according to the present invention
• the charge-transporting pigment particles can be hole-transporting pigment particles.
• the charge-transporting layer can be formed by applying a coating liquid for charge- transporting layer prepared by dissolving a charge- transporting material and a binder resin in a solvent and drying the resulting coating.
• the amount of the charge- transporting material can be 20 to 100 parts by mass, such as 30 to 100 parts by mass, based on 100 parts by mass of the total mass of the charge-transporting material and the binder resin.
• Examples of the charge-transporting material that is used in the charge-transporting layer include polymer compounds having heterocyclic rings or condensed polycyclic aromatic groups such as poly-N-vinylcarbazole and polystyryl anthracene; heterocyclic compounds such as pyrazoline, imidazole, oxazole, triazole, and carbazole; triarylalkane derivatives such as triphenylmethane ; triarylamine
• derivatives such as triphenylamine; and low-molecular-weight compounds such as phenylenediamine derivatives , N- phenylcarbazole derivatives , stilbene derivatives , and hydrazone derivatives .
• binder resin examples include polycarbonate polymers, polyarylate polymers , and polyester polymers .
• a surface protective layer may be disposed on the charge-transporting layer.
• part(s) n in the examples means “part(s) by mass”.
• Polymers Bl to B7 can be synthesized by a method described in, for example, the chapters 1 to 4 of New
• Composition ratio [mass%] (mass of grafted carboxylic acid unit (A2))/(mass of polyolefin polymer) x 100
• composition ratios of polymers other than carboxylic acid unit (A2) were determined by 1 H-NMR and 13 C- MR analyses (manufactured by Varian Inc., 300 MHz) in ortho-dichlorobenzene (d4) at 120° C.
• the measurement was performed by a gate-decoupling method considering the quantitativity .
• a disperser As a disperser, an agitator having a sealable pressure-resistant 1-liter glass container equipped with a heater was used. In this glass container, 75.0 g of BONDINE HX-8290 (polyolefin polymer), 60.0 of isopropanol, 5.1 g of triethylamine , and 159.9 g of distilled water were loaded and stirred at a rotational speed of the impeller of 300 rpm. As a result, no precipitation of the polymer particular substance was confirmed on the bottom of the container, and a floating state of the polymer was confirmed. This state was maintained for 10 minutes, and then the heater was turned on to heat the mixture.
• BONDINE HX-8290 polyolefin polymer
• a polyolefin polymer particle dispersion solution (2) was obtained in the same manner as in Preparation
• an agitator having a sealable pressure-resistant 1-liter glass container provided with a heater was used.
• this glass container 60.0 g of BONDINE AX-8390 (polyolefin polymer), 100.0 g of n-propanol, 2.5 g of triethylamine , and 137.5 g of distilled water were loaded and stirred at a rotational speed of the impeller of 300 rpm.
• no precipitation of the polymer particular substance was confirmed on the bottom of the container, and a floating state of the polymer was confirmed. This state was maintained for 10 minutes, and then the heater was turned on to heat the mixture. Stirring was continued for another 20 minutes while maintaining the system temperature at 120° C. Then, the container was cooled to room
• dispersion solution (1) in such a manner that the solid content (polyolefin polymer particles and charge- transporting pigment particles) in the resulting mixture was 10 mass%.
• This solution mixture was subjected to dispersion treatment in a sand mill using glass beads having a diameter of 1 mm for 12 hours to obtain dispersion solution (1) for charge-transporting layer.
• the particles composed of the polyolefin polymer particles and the charge-transporting pigment particles contained in the resulting dispersion solution (1) for charge-transporting layer had a number average particle diameter of 120 nm and a degree of dispersion (standard deviation/number average particle diameter) of 0.6.
• the dispersion solution (1) for charge-transporting layer was applied onto an aluminum sheet by dipping, and the resulting coating was dried at 100° C for 30 minutes to obtain a charge-transporting layer having a thickness of 1.0 ⁇ .
• the dispersion state of the charge-transporting pigment particles in the charge-transporting layer was evaluated by observing a cross-section of the charge- transporting layer using a transmission electron microscope (TEM) based upon the following criteria:
• Charge-transporting layers were formed in the same manner as in Formation Example 1 of charge-transporting layer except that charge-transporting pigment particles shown in Tables 2 and 3 were used instead of the charge- transporting pigment particles (E116) in Formation Example 1, and the layers were evaluated. The results are shown in Tables 2 and 3
• Charge-transporting layers were formed in the same manner as in Formation Example 1 of charge-transporting layer except that polyolefin polymer particle dispersion solutions (2) to (11) were used instead of the polyolefin polymer particle dispersion solution (1) in Formation
• Example 1 Example 1, and the layers were evaluated. The results are shown in Table 2.
• a solution mixture was prepared by adding a
• dispersion medium (medium mixture) composed of
• polyolefin polymer particle dispersion solution (1) in such a manner that the solid content (polyolefin polymer particles and charge-transporting pigment particles) in the resulting mixture was 2 mass%.
• This solution mixture was subjected to dispersion treatment in a sand mill using glass beads having a diameter of 1 mm for 2 hours to obtain dispersion solution (CI) for charge-transporting layer.
• the resulting dispersion solution (CI) for charge- transporting layer was applied to an aluminum sheet, and the resulting coating was dried at 100° C for 30 minutes to obtain a charge-transporting layer having a thickness of 1.0 ⁇ .
• the dispersion medium medium mixture
• the solid content polyolefin polymer particles and charge-transporting pigment particles
• a polymer solution was prepared by dissolving 10 parts of N-methoxy methylated 6 nylon in 90 parts of methanol. To this polymer solution, 10 parts of charge- transporting pigment particles (E116) and 90 parts of
• dispersion solution (C4) for charge-transporting layer.
• the resulting dispersion solution (C4) for charge- transporting layer was applied to an aluminum sheet, and the resulting coating was dried at 100° C for 30 minutes to obtain a charge-transporting layer having a thickness of 1.0 ⁇ .
• a polymer solution was prepared by dissolving 10 parts of a polyvinyl butyral polymer in 80 parts of butanol. To this polymer solution, 10 parts of charge-transporting pigment particles (E116) and 90 parts of methanol were added, and the resulting mixture was subjected to dispersion
• dispersion solution (C5) for charge-transporting layer.
• the resulting dispersion solution (C5) for charge- transporting layer was applied to an aluminum sheet, and the resulting coating was dried at 100" C for 30 minutes to obtain a charge-transporting layer having a thickness of 1.0 ⁇ .
• the resulting charge-transporting layer was evaluated as in Formation Example 1 of charge-transporting layer. The results are shown in Table 3. The appearance of the dispersion solution for charge-transporting layer was observed to confirm that the polyvinyl butyral polymer was completely dissolved not to have particle shapes.
• water fraction [mass%] means the amount of water (ratio) [mass%] in a dispersion solution based on the total mass of water and alcohol in the dispersion solution.
• solid fraction means the amount of water (ratio) [mass%] in a dispersion solution based on the total mass of water and alcohol in the dispersion solution.
• fraction [mass*] means the sum (ratio) of the amount of polyolefin polymer particles and the amount of charge- transporting pigment particles in a dispersion solution based on the total mass of the dispersion solution.
• TITANIX JR manufactured by Tayca Corp.
• 25 parts of a phenol polymer as a binder resin (trade name: Plyophen J-325, manufactured by DIC Corp., polymer solid content: 60 mass%)
• 30 parts of methoxypropanol and 30 parts of methanol were mixed, and the resulting mixture was subjected to dispersion treatment in a sand mill using glass beads having a diameter of 1 mm for 2 hours.
• silicone polymer particles serving as a surface roughness -providing material (trade name: Tospearl 120, manufactured by GE Toshiba Silicone Co., Ltd., average particle diameter: 2 pirn) and 0.002 parts of silicone oil as a leveling agent (trade name: SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.) were added, followed by stirring to prepare a coating liquid for conductive layer.
• the coating liquid for conductive layer was applied to the support by dipping under an environment of 23"C/60% RH.
• the resulting coating was dried and thermally cured at 140° C for 30 minutes to obtain a conductive layer having a thickness of 20 ⁇ .
• the dispersion solution (1) for charge- transporting layer was applied onto the conductive layer by dipping, and the resulting coating was heated at 100° C for 30 minutes to melt the polyolefin polymer particles and thereby form a charge-transporting layer (electron- transporting layer) as an undercoat layer having a thickness of 1.0 ⁇ .
• phthalocyanine crystals charge-generating material in a crystal form showing main peaks at Bragg angles, 2 ⁇ 0.2° , of 7.5°, 9.9°, 16.3°, 18.6°, 25.1°, and 28.3° in the CuKa characteristic X-ray diffraction, 5 parts of a polyvinyl butyral polymer (trade name: S-LEC BX-1, manufactured by Sekisui Chemical Co., Ltd.), 0.1 parts of a compound
• a coating liquid for charge-transporting layer was prepared by dissolving 10 parts of a compound (charge- transporting material (hole-transporting compound) )
• This coating liquid for charge- transporting layer was applied onto the charge-generating layer by dipping, and the resulting coating was dried at 120" C for 1 hour to obtain a charge-transporting layer (hole-transporting layer) having a thickness of 12 ⁇ .
• photosensitive member was left under an environment of an ordinary temperature and an ordinary humidity (23.5°C/50% RH) for 24 hours and was then evaluated for
• the electrophotographic characteristics were evaluated as follows: First, the developing unit was detached from a laser beam printer (trade name: Laser Jet 4600, manufactured by Hewlett-Packard Company) modified so that the light intensity was variable, and instead a laser beam printer (trade name: Laser Jet 4600, manufactured by Hewlett-Packard Company) modified so that the light intensity was variable, and instead a laser beam printer (trade name: Laser Jet 4600, manufactured by Hewlett-Packard Company) modified so that the light intensity was variable, and instead a
• Electrophotographic photosensitive members were produced as in Example 1 except that dispersion solution (2), (7), (11), (23), or (26) for charge-transporting layer was used for forming a charge-transporting layer (electron- transporting layer) serving as the undercoat layer, instead of dispersion solution (1) for charge-transporting layer in Example 1 , and the electrophotographic photosensitive
• the dispersion solution (1) for charge- transporting layer was applied to the support by dipping, and the resulting coating was heated at 100° C for 30 minutes to melt the polyolefin polymer particles and thereby obtain a charge-transporting layer (electron-transporting layer) having a thickness of 1.0 ⁇ as the undercoat layer.
• Example 2 a charge-generating layer and a charge-transporting layer (hole-transporting layer) were formed on the charge-transporting layer (electron- transporting layer) serving as the undercoat layer to produce an electrophotographic photosensitive member.
• An electrophotographic photosensitive member was produced as in Example 1 except that an undercoat layer formed as shown below was used instead of the charge- transporting layer (electron-transporting layer) as the undercoat layer in Example 1 and was evaluated. The results are shown in Table 4.
• a coating liquid for undercoat layer was prepared by dissolving 5 parts of N-methoxy methylated 6 nylon in 95 parts of methanol. This coating liquid for undercoat layer was applied onto the conductive layer by dipping, and the resulting coating was dried at 100° C for 30 minutes to form an undercoat layer having a thickness of 1.0 ⁇ .

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